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United States Patent |
5,281,541
|
Saito
,   et al.
|
January 25, 1994
|
Method for repairing an electrically short-circuited semiconductor
device, and process for producing a semiconductor device utilizing said
method
Abstract
A method for repairing a defective semiconductor device, the defective
semiconductor device including a semiconductor thin film and a conductive
thin film, disposed in the named order, on a conductive surface of a
substrate, such that the conductive thin film and the conductive surface
of the substrate are electrically short-circuited at a pinhole occurring
in the semiconductor thin film to form an electrically short-circuited
portion. The method includes the steps of applying desired a voltage
through an electrode positioned above a surface of the defective
semiconductor device, and moving the electrode along the surface of the
defective semiconductor device while maintaining a distance between the
electrode and the conductive thin film sufficient to allow a discharge to
occur when the electrode is above the electrically short-circuited
portion, such that the discharge modifies a region of the conductive thin
film which is in electrical contact with the conductive surface of the
substrate, to establish an electrically noncontacted state between the
conductive thin film and the conductive surface of the substrate.
Inventors:
|
Saito; Keishi (Nagahama, JP);
Aoike; Tatsuyuki (Nagahama, JP);
Niwa; Mitsuyuki (Nagahama, JP);
Kariya; Toshimitsu (Nagahama, JP);
Koda; Yuzo (Nagahama, JP)
|
Assignee:
|
Canon Kabushiki Kaisha (Tokyo, JP)
|
Appl. No.:
|
755439 |
Filed:
|
September 5, 1991 |
Foreign Application Priority Data
Current U.S. Class: |
438/4; 136/258; 136/290; 257/E21.158; 257/E31.042; 257/E31.126; 438/63; 438/88; 438/466 |
Intern'l Class: |
H01L 021/306 |
Field of Search: |
437/2,4,5,170,923
|
References Cited
U.S. Patent Documents
4400409 | Aug., 1983 | Izu et al. | 427/39.
|
4438723 | Mar., 1984 | Cannella et al. | 118/718.
|
4438724 | Mar., 1984 | Doehler et al. | 118/719.
|
4774193 | Sep., 1988 | Juergens | 437/923.
|
4806496 | Feb., 1989 | Suzuki et al. | 437/923.
|
4812415 | Mar., 1989 | Yamazaki et al. | 437/923.
|
Foreign Patent Documents |
0073713 | Mar., 1983 | EP.
| |
0256180 | Feb., 1988 | EP.
| |
60-43871 | Mar., 1985 | JP.
| |
62-59901 | Dec., 1987 | JP | .
|
63-88869 | Apr., 1988 | JP.
| |
Primary Examiner: Fourson; George
Attorney, Agent or Firm: Fitzpatrick, Cella, Harper & Scinto
Claims
What is claimed is:
1. A method for repairing a defective semiconductor device, the defective
semiconductor device including a semiconductor thin film and a conductive
thin film, disposed in the named order, on a conductive surface of a
substrate, such that the conductive thin film and the conductive surface
of the substrate are electrically short-circuited at a pinhole occurring
in the semiconductor thin film to form an electrically short-circuited
portion, said method comprising the steps of:
(a) applying a desired voltage through an electrode positioned above a
surface of the defective semiconductor device; and
(b) moving the electrode along the surface of the defective semiconductor
device while maintaining a distance between the electrode and the
conductive thin film sufficient to allow a discharge to occur when the
electrode is above the electrically short-circuited portion, such that the
discharge modifies a region of the conductive thin film which is in
electrical contact with the conductive surface of the substrate to
establish an electrically noncontacted state between the conductive thin
film and the conductive surface of the substrate.
2. The method according to claim 1, wherein the substrate comprises a metal
base member and another conductive thin film formed on the metal base
member.
3. The method according to claim 1, wherein the substrate comprises an
insulating base member and another conductive thin film formed on the
insulating base member.
4. The method according to claim 1, wherein the electrode is continuously
moved above the semiconductor device while leaving a distance between the
conductive thin film and the electrode.
5. The method according to claim 1, wherein the electrode is continuously
moved in a first direction above the semiconductor device while leaving a
distance between the conductive thin film and the electrode, and wherein
the semiconductor device is intermittently moved in a second direction
perpendicular to the first direction.
6. The method according to claim 1, wherein the semiconductor device
comprises a continuous semiconductor device comprising the semiconductor
thin film and the conductive thin film being disposed in the named order
on a conductive surface of a continuous substrate.
7. The method according to claim 6, wherein the electrode comprises a
plurality of probes being arranged at equal intervals above the continuous
semiconductor device, and wherein the continuous semiconductor device is
continuously moved in a lengthwise direction thereof.
8. The method according to claim 1, wherein the semiconductor device
comprises a pin junction photovoltaic element.
9. The method according to claim 1, wherein the semiconductor thin film of
the semiconductor device includes a silicon-containing semiconductor film.
10. The method according to claim 1, wherein the conductive thin film of
the semiconductor device includes a layer region comprising a material
selected from the group consisting of MgF.sub.2, ZnO, TiO.sub.2, In.sub.2
O.sub.3, SnO.sub.2, and ITO.
11. The method according to claim 1, wherein the conductive thin film of
the semiconductor device includes a layer region comprising a material
selected from the group consisting of Ag, Al, and Cr.
12. A process for producing a semiconductor device comprising the steps of:
(a) providing a substrate having a conductive surface;
(b) forming a semiconductor thin film and a conductive thin film, in the
named order, on the conductive surface of the substrate to prepare the
semiconductor device;
(c) applying a desired voltage through an electrode positioned above the
semiconductor device, and
(d) moving the electrode along a surface of the semiconductor device while
maintaining a distance between the electrode and the conductive thin film
sufficient to allow a discharge to occur when the electrode is above a
region of the conductive thin film in electrical contact with the
conductive surface of the substrate, such that the discharge modifies the
region to establish an electrically noncontacted state between the
conductive thin film and the conductive surface of the substrate.
Description
BACKGROUND OF THE INVENTION
1. Field of the invention
The present invention relates to a method for repairing an electrically
short-circuited semiconductor device by insulating portions of the device
which are short-circuited due to pin holes and the like, an apparatus
suitable for practicing said method, and a process for producing a
semiconductor device by utilizing said method.
2. Related background art
In recent years, various studies have been made on large area semiconductor
devices such as solar cell, flat panel display, photosensor,
electrophotographic photosensitive device, etc. In addition, the public
attention has been focused on non-single crystal semiconductors such as
amorphous silicon semiconductors to constitute those large area
semiconductor devices mainly because of their reasonable production cost.
For instance, there is known a pin junction type amorphous silicon solar
cell as an example of such non-single crystal semiconductor device. In
this solar cell, photocarriers occur in its semiconductor layer,
comprising an amorphous silicon semiconductor thin film, when light is
impinged in the solar cell. The photocarriers migrate to its transparent
electrode comprising a transparent conductive thin film situated on the
side through which light is impinged and also to its conductive substrate
situated opposite the transparent electrode by the action of an internal
electric field, to thereby provide a photoelectromotive force.
The conductive thin film serving as the transparent electrode and the
semiconductor thin film serving as the photosensitive semiconductor layer
may be properly formed in a vacuum chamber in accordance with a plasma CVD
method, a photo CVD method, a thermal CVD method, a vacuum evaporation
method, or a sputtering method.
In the preparation of such amorphous silicon solar cell, due regard should
be made to the problem relating to a short circuit which is often caused
between the transparent electrode and the conductive substrate due to
pinholes occurring at part of the semiconductor layer.
There are various causes for such pinholes to occur. For instance, in one
case, since the transparent electrode is usually of some hundreds of
angstrom in thickness and the semiconductor layer is usually of about
0.005 to some tens of um, minute dust particles (some micrometer to some
tens micrometer in size) are deposited on the surface of the conductive
substrate or they are deposited on or contaminated into the semiconductor
layer during film formation to cause a removal for the conductive
substrate or/and the semiconductor layer, whereby such pinholes occur at
the semiconductor layer.
In other case, such pinholes are occurred when part of the semiconductor
layer is removed due to its internal stress or its insufficient adhesion
with the transparent electrode to furnish the conductive substrate with a
region not having a desired semiconductor layer. In this case, the
transparent electrode situated on the side through which light is impinged
and the conductive substrate situated opposite said electrode are
connected with each other through said region to be in an electrically
short-circuited state. This results in significantly degrading of the
characteristics required for a semiconductor device.
The occurrence of pinholes causing a short circuit is a serious problem
particularly in the case of a large area semiconductor device such as
solar cell, flat panel display, photosensor, electrophotographic
photosensitive device, etc. In any case, it is extremely difficult to
obtain a large area semiconductor device completely free of a
short-circuited state region even under a clean environment substantially
free of minute dust particles.
In order to solve the above problem relating to occurrence of pinholes
causing a short circuit, Japanese Patent Publication 62(1987)-53958
(hereinafter referred to as Literature 1) proposes a method of making the
inside of each of the pinholes occurring at the thin film semiconductor
layer of a photosemiconductor to be in an electrically insulating state by
perforating pinholes at its electrode layer and communicating the pinholes
of the thin film semiconductor layer with the pinholes of the electrode
layer. Likewise, Japanese Patent Publication No. 62(1987)-59901
(hereinafter referred to as Literature 2) proposes a method of reclaiming
pinholes occurring at the thin film semiconductor layer of a semiconductor
device by fusing the peripheries of the pinholes with radiation of energy
beam.
FIGS. 10(A) and 10(B) are schematic views respectively for explaining the
method according to Literature 1.
In FIGS. 10(A) and 10(B), numeral reference 1 stands for a translucent
substrate, numeral reference 2 stands for a translucent electrode layer,
numeral reference 3 stands for a semiconductor layer comprising a thin
semiconductor film, numeral reference 4 stands for a back electrode layer,
numeral reference 5 stands for a pinhole in a short-circuited state,
numeral reference 6 stands for a pinhole provided at the back electrode
layer, numeral reference 7 stands for laser beam, and numeral reference 8
stands for laser beam.
The method according to Literature 1 is to be explained with reference to
FIGS. 10(A) and 10(B). That is, after a plurality of semiconductor devices
have been prepared, semiconductor devices defective due to a short circuit
are sorted out. As for each of those defective semiconductor devices, beam
plane-scanning is performed while irradiating laser beam 7 through the
other principal face of the translucent substrate 1 as shown in FIG.
10(A). When a short circuit current is measured for the semiconductor
device at the time of performing the beam plane-scanning a, short circuit
current does not flow when the laser beam 7 is irradiated to the portion
where a pinhole 5 in a short-circuited state is present, and on the other
hand, upon irradiating the laser beam 7 to the other portion where such
short-circuited state is not present, a hole-electron pair is caused and
migrates in the semiconductor layer 3, whereby a short circuit current
flows. In view of this, the position where a pinhole 5 is present can be
found for the semiconductor device by performing plane-scanning using the
laser beam 7.
As for the portion of the semiconductor layer where a pin hole 5 is
present, laser beam outputted from YAG pulse laser of 5.times.10.sup.6
W/cm.sup.2 in peak outputting power is radiated through the back electrode
layer 4 in the way as shown by an arrow 8 to thereby remove a
short-circuited state region comprising the constituent of the back
electrode layer 4 which is extended to the inside of the pinhole 5.
Particularly, as shown in FIG. 10(B), a pinhole 6 is made at the back
electrode layer 4 formed on the semiconductor layer 3 having the pinhole 5
occurring therethrough at the time of the formation thereof such that it
is coaxially in communication with the pinhole 5, whereby the inside of
the pinhole 5 and that of the pinhole 6 are made to be in an electrically
insulating state.
FIGS. 10(C), 10(D) and 10(E) are schematic views for explaining the method
according to Literature 2.
In FIGS. 10(C), 10(D) and 10(E), numeral reference 1 stands for a
translucent substrate, numeral reference 2 stands for a translucent
electrode layer, numeral reference 3 stands for a semiconductor layer
comprising a thin semiconductor film, numeral reference 4 stands for a
back electrode layer, numeral reference 5 stands for a pinhole in a
short-circuited state, numeral reference 7 stands for laser beam, and
numeral reference 9 stands for a photosensor.
The method according to Literature 2 is to be explained with reference to
FIGS. 10(C) through 10(E).
That is, a translucent electrode 2 is formed on a translucent substrate 1
and then, a thin film semiconductor layer 3 is formed on the translucent
electrode 2. As for the device thus obtained, it is examined whether or
not the semiconductor layer 3 is accompanied with a pinhole 5, by
plane-scanning is performed for the semiconductor layer 3 while
irradiating laser beam 7 outputted from an Ar gas laser of an extremely
low outputting power through the rear side of the semiconductor layer 3
and moving a photosensor 9 arranged on the side of the translucent
substrate 1 and opposite the Ar gas laser in synchronism with the scanning
of the laser beam 7 in the way as shown in FIG. 10(C), to thereby examine
whether or not the semiconductor layer 3 is accompanied with a pinhole 5.
In this case, if such pinhole 5 is not present at the portion of the
semiconductor layer 3 where the laser beam 7 is irradiated, the laser beam
7 is absorbed by the semiconductor 3 and does not reach the photosensor 9.
On the other hand, if such pinhole 5 is present at the portion of the
semiconductor layer 3 where the laser beam 7 is irradiated, the laser beam
7 reaches the photosensor 9, and from a signal outputted from the
photosensor 9 at that time, the position where the pinhole 5 is present is
detected.
When the presence of the pinhole 5 is optically detected as above
described, laser beam of about 2 to 3 W/cm.sup.2 in power outputted from,
for example, an Ar gas laser of 514.5 nm in oscillating wavelength instead
of the laser beam 7 is irradiated to the portion where the pinhole 5 is
present to thereby fuse the peripheries of the pinhole 5 with respect to
the semiconductor layer 3, whereby the pinhole 5 is filled up with the
constituent of the semiconductor layer 3 in such a state as shown in FIG.
10(D). The filled portion of the semiconductor layer 3 exhibits a fused
state at the beginning but it is sooner or later cooled, wherein the
constituent of the filled portion is changed from amorphous state to
polycrystalline state or the like and the junction state is eventually
broken. Thus, the filled portion finally becomes to function substantially
as an insulator.
Finally, as shown in FIG. 10(E), a 2000 to 10000 thick aluminum layer
serving as a back electrode 4 is laminated on the semiconductor layer 3
having the above filled portion by a vacuum evaporation technique.
The above mentioned two methods are effective in order to solve the
foregoing problems relating to short circuit caused due to pinholes
occurring at the semiconductor layer to a certain extent, but there still
exist such problems as will be mentioned below, which are necessary to be
solved.
In the case of the method according to Literature 1, there is a problem
that it takes a long period of time in order to detect a number of
pinholes being present at the semiconductor layer of a large area by way
of the laser beam scanning process.
There is also other problem for the method according to Literature 1 that,
in this method, as apparent from FIG. 10(B), the pinhole 6 is left as it
is in any case, however, such pinhole must be filled up in practice. That
is, in the case of a semiconductor device having such a configuration as
shown in FIG. 10(B) in which the pinhole 6 is left without being filled
up, water, alkaline metal, or the like are apt to enter therethrough upon
use, and once water or/and alkaline metal, etc. have entered thereinto,
the semiconductor device will be deteriorated shortly. However, in order
to fill up such pinhole as shown in FIG. 10(B), not only a specific
technique is required but also it takes time, and because of this, the
resulting product becomes unavoidably costly.
Likewise, there are some problems also for the method according to
Literature 2. That is, in the case of the method according to Literature
2, as apparent from what shown in FIG. 10(D), the pinhole 6 is filled up
by fusing the peripheries thereof, but this process is performed prior to
forming the back electrode layer 4, and because of this, a pinhole which
will be caused at the time of forming the back electrode layer on the
semiconductor layer 3 having the filled portion is unavoidably, left
without being filled up. In addition to this, since the fill up of the
pinhole 5 is performed through the laser beam-irradiating process which
takes time while exposing the semiconductor layer 3 to environmental
atmosphere, the quality of the semiconductor 3 is apt to deteriorate
during the filling up process.
There is a still further problem for the method according to Literature 2
in that it takes a long period of time in order to detect a number of
pinholes being present at the semiconductor layer of a large area by way
of the laser beam scanning process and it is extremely difficult to fill
up all such numerous pinholes uniformly by way of the laser beam fusing
process.
In view of the above, in the case of the method according to Literature 2,
if a desirable semiconductor device should be obtained, it will be costly.
SUMMARY OF THE INVENTION
A principal object of the present invention is to eliminate the foregoing
problems in the prior art and to provide an improved method which enables
to efficiently repair a short-circuited portion of a semiconductor device
within a short period of time without performing such detecting process as
in the prior art.
Other object of the present invention is to provide an apparatus suitable
for practicing said improved method.
A further object of the present invention is to provide a process for
producing an improved semiconductor device utilizing said improved method.
A still further object of the present invention is to provide an improved
method for repairing a defective semiconductor device having an
electrically short-circuited portion, comprising a semiconductor thin film
and a transparent and conductive thin film being disposed in this order on
a surface of a conductive substrate in which said transparent and
conductive thin film and said conductive substrate are electrically
short-circuited due to pinholes occurring at part of said semiconductor
thin film, to form a desirable semiconductor device free of such
short-circuited portion which functions as originally desired for the
semiconductor device.
A still further object of the present invention is to provide a method
which enables to efficiently repair a short-circuited portion of the
constituent semiconductor member of a photovoltaic element within a short
period of time without performing such detecting process as in the prior
art to obtain a desirable photovoltaic element which is markedly improved
with respect to short circuit current and open-circuit voltage and which
stably provides a desirable photoelectric conversion efficiency without
being deteriorated even upon repeated use for a long period of time.
The present invention effectively attains the above objects and it includes
a method for repairing a defective semiconductor device to result in a
desirable semiconductor device, an apparatus suitable for practicing said
method and a process for producing a semiconductor device utilizing said
method.
The method for repairing a defective semiconductor device according to the
present invention is of the constitution which will be under described.
That is, a method for repairing a defective semiconductor device having an
electrically short-circuited portion which comprises a semiconductor thin
film and a conductive thin film being disposed in this order on a
conductive surface of a substrate in which said conductive thin film and
said conductive surface of substrate are electrically short-circuited due
to pinholes occurring at part of said semiconductor thin film. A desired
voltage is applied through a probe arrange over said electrically
short-circuited portion while leaving a predetermined distance between
said probe and said conductive thin film to cause discharge between said
semiconductor device and said probe, whereby a region of said conductive
thin film in electrical contact with the surface of said conductive
surface of substrate is modified to establish an electrically noncontacted
state between said conductive thin film and said conductive surface.
The apparatus suitable for practicing the above method according to the
present invention is of the constitution which will be described below.
That is, an apparatus for repairing a defective semiconductor device having
an electrically short-circuited portion which comprises a semiconductor
thin film and a conductive thin film being disposed in this order on a
conductive surface of a substrate in which said conductive thin film and
said conductive substrate are electrically short-circuited due to pinholes
occurring at part of said semiconductor thin film, said apparatus
comprises:
a substrate holding means on which said substrate is to be positioned;
a probe being arranged over said semiconductor device positioned through
its substrate on said substrate holding means while leaving a
predetermined distance between said probe and said conductive thin film of
the semiconductor device, said probe being capable of moving in relation
to said substrate of the semiconductor device; and
a voltage applying means for applying a desired voltage between said prove
and said conductive surface of substrate; wherein discharge is caused
between said probe and said conductive thin film by applying a desired
voltage between said probe and said conductive surface of substrate
through said voltage applying means to thereby modify a region of said
conductive thin film in electrical contact with the surface of said
conductive surface of substrate, whereby establishing an electrically
noncontacted state between said conductive thin film of the semiconductor
device and said conductive surface of substrate.
The process for producing a semiconductor device according to the present
invention is of the constitution which will be described below.
That is, a process for producing a semiconductor device which comprises the
steps of:
(a) positioning a substrate having a conductive surface on a substrate
holding means in a deposition chamber;
(b) forming a semiconductor thin film and a conductive thin film in this
order on said conductive surface of the substrate to prepare a
semiconductor device;
(c) applying a desired voltage through a probe arranged over said
semiconductor device while leaving a predetermined distance between said
probe and said conductive thin film of the semiconductor device to cause
discharge between said semiconductor device and said probe, whereby a
region of said conductive thin film in electrical contact with the surface
of said conductive surface of substrate is modified to establish an
electrically noncontacted state between said conductive thin film and said
conductive surface.
In the present invention, the probe is desired to continuously move over
the semiconductor device while maintaining a predetermined distance
between the probe and the conductive thin film of the semiconductor device
upon causing discharge to fuse a portion of the conductive thin film in
order to establish the foregoing electrically noncontacted state.
In a preferred embodiment, the process of establishing the foregoing
electrically noncontacted state is performed by moving the probe in a
predetermined direction over the semiconductor device while maintaining a
predetermined distance between the probe and the conductive thin film of
the semiconductor device and at the same time, intermittently moving the
conductive substrate of the semiconductor device in a direction
rectangular, or perpendicular, to said predetermined direction with
respect to the probe.
In the case of repairing a large area semiconductor device in the present
invention, it is possible to arrange a plurality of probes at an equal
interval over the semiconductor device while leaving a predetermined
distance between each of the probes and the conductive thin film and move
the semiconductor device to be repaired in a lengthwise direction of said
plurality of probes.
As for the process of establishing the foregoing electrically noncontacted
state, it is desired to be performed in a predetermined gaseous
atmosphere. For instance, in a preferred embodiment, it is performed in a
substantially enclosed vessel capable of vacuuming its inside containing
one or more probes and a substrate holding means while supplying an
appropriate gas such as clean air or other gas containing oxygen atoms or
nitrogen atoms thereinto.
According to the present invention, a desirable semiconductor device
satisfactory in the semiconductor characteristics required therefor can be
efficiently produced with an improved yield.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a schematic cross section view for explaining a defective
semiconductor device having a short-circuited portion caused due to a
pinhole.
FIG. 2 is a schematic diagram of an apparatus suitable for practicing a
first embodiment of the method for repairing a defective semiconductor
device, according to the present invention.
FIG. 3 is a schematic cross section view of a desirably repaired
semiconductor device in accordance with the method for repairing a
defective semiconductor device, according to the present invention.
FIG. 4 is a schematic diagram of an apparatus suitable for practicing a
second embodiment of the method for repairing a defective semiconductor
device, according to the present invention.
FIG. 5 is a schematic diagram of an apparatus suitable for practicing a
second embodiment of the method for repairing a defective semiconductor
device, according to the present invention.
FIG. 6(A) is a graph showing current/voltage characteristics of a
semiconductor device in which a short-circuited portion is present and
which does not have a diode property; and FIG. 6(B) is a graph showing
current/voltage characteristics of a semiconductor device in which the
short-circuited portion has been repaired and which has a diode property.
FIG. 7 is a schematic explanatory view of a solar cell as the semiconductor
to be produced according to the present invention.
FIG. 8 is a schematic explanatory view of a photosensor as the
semiconductor to be produced according to the present invention.
FIGS. 9(A), 9(B) and 9(C) are schematic views respectively for explaining
the process for preparing the photosensor shown in FIG. 8.
FIGS. 10(A), 10(B), 10(C), 10(D) and 10(E) are schematic views respectively
for explaining a conventional method of repairing a defective
semiconductor device.
FIGS. 11 and 12 are schematic views for explaining other conventional
methods of repairing a defective semiconductor device.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
The semiconductor device which can be repaired in accordance with the
repairing method of the present invention can include solar cells, flat
panel displays, photosensors, electrophotographic photosensitive members,
electron emission elements, luminescent elements, etc.
The repairing method of the present invention is particularly effective in
repairing defective solar cells among others.
In view of this, an explanation is to be made with respect to the case of
repairing a defective solar cell by the repairing method of the present
invention.
Shown in FIG. 1 is a schematic cross section view of an example of such
defective solar cell.
In FIG. 1, numeral reference 101 stands for the entire of a so-called
single cell type solar cell which is of the constitution comprising a
single cell with a pin junction being disposed between a conductive
substrate and a transparent conductive thin film and which is
short-circuited. Numeral reference 102 stands for a conductive substrate
comprising a conductive thin film 102bbeing laminated on a conductive or
insulating base member 102a. Numeral reference 103 stands for a
photoelectric conversion layer comprising a pin junction semiconductor
layer which is disposed on the conductive thin film 102b of the conductive
substrate 102. Numeral reference 104 stands for a conductive thin film
being laminated on the photoelectric conversion layer 103. Numeral
reference 105 stands for a collecting electrode being disposed on the
conductive thin film 104.
In the case where the solar cell 101 is of the type that light is impinged
from the side of the conductive thin film 104, the conductive thin film
104 is made to be a transparent and conductive thin film composed of a
transparent and conductive material, and at least either the base member
102a or the conductive thin film 102b is composed of an opaque material.
In the case where the solar cell 101 is of the type that light is impinged
from the conductive substrate 102, the base member 102a is composed of a
translucent material and the conductive thin film 102b is composed of a
transparent and conductive material. As for the transparent and conductive
thin film 104 in this case, it should be changed to be an opaque and
conductive thin film.
Each of numeral references 106a and 106b stands for a pinhole occurring at
the pin junction semiconductor layer (photoelectric conversion layer) 103,
wherein 106a indicates a pinhole caused due to removal occurring at the
pin junction semiconductor layer 103, and 106b indicates a pinhole caused
due to removal occurring at the transparent conductive thin film 104 and
the pin junction semiconductor layer 103.
In any of these two cases, there is present a short-circuited portion
between the transparent conductive thin film 104 and the conductive
substrate 102, and because of this, the solar cell is defective since it
is in a short-circuited state and can not generate a photoelectromotive
force as desired.
Other than the above, the repairing method of the present invention can be
applied in repairing other short-circuited solar cells having a plurality
of pin junction cell units being stacked between a conductive substrate
and a transparent conductive thin film.
Explanation is to be made about the above mentioned short-circuited
defective solar cell which can be repaired according to the present
invention.
Conductive Substrate 102
The conductive substrate 102 may be comprised only of a conductive member
having a conductive surface which is made of a metal such as stainless
steel, aluminum, etc.
In an alternative, the conductive substrate 102 may be a member comprising
a conductive or insulating base member 102a made of a metal such as
stainless steel, aluminum, etc. or an insulating material such as glass,
quartz, synthetic resin, etc. which is applied with a conductive thin film
102b comprising MgF.sub.2, ZnO, TiO.sub.2, ITO (In.sub.2 O.sub.3
+SnO.sub.2), In.sub.2 O.sub.3, SnO.sub.2, Ag, Al, Cr or the like to the
surface thereof by a vacuum evaporation method or a sputtering method. The
conductive thin film 102b may be a multilayered thin film comprising a
plurality of thin films of MgF.sub.2, ZnO, TiO.sub.2, ITO (In.sub.2
O.sub.3 +SnO.sub.2), In.sub.2 O.sub.3, SnO.sub.2, Ag, Al, Cr or the like
being stacked.
Photoelectric Conversion Layer 103 (Pin Junction Semiconductor Layer)
The photoelectric conversion layer 103 may be a pin junction semiconductor
thin film comprising a non-single crystal material containing silicon
atoms as the main constituent such as silicon-containing amorphous
materials e.g. amorphous silicon, amorphous silicon carbide or amorphous
silicon germanium, microcrystalline silicon materials or polycrystalline
silicon materials which can be formed by a plasma CVD method, a light CVD
method, a thermal CVD method, a vacuum evaporation method, a sputtering
method or an annealing method. In an alternative, the photoelectric
conversion layer 103 may be a pin junction semiconductor thin film
comprising CdS, CdTe, CuInSe.sub.2 or the like which can be formed by a
vacuum evaporation method or a screen printing method.
Conductive Thin Film 104
The conductive thin film 104 may be a single conductive thin film
comprising MgF.sub.2, ZnO, TiO.sub.2, ITO (In.sub.2 O.sub.3 +SnO.sub.2),
In.sub.2 O.sub.3, SnO.sub.2, Ag, Al, Cr or the like which is formed by a
vacuum evaporation method or a sputtering method. In an alternative, the
conductive thin film 104 may be a multilayered thin film comprising a
plurality of thin films of MgF.sub.2, ZnO, TiO.sub.2, ITO (In.sub.2
O.sub.3 +SnO.sub.2), In.sub.2 O.sub.3, SnO.sub.2, Ag, Al, Cr or the like
being stacked which is formed by a vacuum evaporation method or a
sputtering method.
In the process of preparing such solar cell as above mentioned, one or more
pinholes are unavoidably caused in such a state as shown in FIG. 1.
That is, in the case of preparing such solar cell as above mentioned, for
instance, an about 1.0 .mu.m thick ZnO thin film as the conductive thin
film 102b is formed on a stainless steel plate as the base member by a
sputtering method. Then, an about 0.5 .mu.m thick pin junction
photoelectric conversion semiconductor layer (solar cell element)
comprising a non-single crystal Si thin film as the pin junction
semiconductor layer 103 is formed on the ZnO thin film by a plasma CVD
method. Successively, an about 0.07 .mu.m thick indium oxide thin film as
the transparent and conductive thin film 104 is formed on the pin junction
photoelectric conversion semiconductor layer by a vacuum evaporation
method.
In this case, one or more pinholes are unavoidably caused within the
resulting device as shown in FIG. 1. That is, such pinholes indicated by
106a and 106b are caused during the process of forming the pin junction
semiconductor layer 103. Specifically, these pinholes are caused due to
removal of the pin junction semiconductor layer 103 from the conductive
thin film 102b which occurrs as a result of depositing minute dusts
removed from the materials of the plasma CVD deposition chamber
circumscribing the film-forming space on the surface of the conductive
substrate 102 (specifically, the conductive thin film 102b) upon forming
the pin junction semiconductor layer 103. Other than this, these pinholes
are also caused due to removal of a partial layer region of the pin
junction semiconductor layer 103 from the conductive substrate 102
(specifically, the conductive thin film 102b) because of an internal
stress of said semiconductor layer or because of poor adhesion of said
semiconductor layer with the conductive substrate 102.
Further in addition, these pinholes are caused in the case of forming a
transparent and conductive thin film 104 on the previously formed pin
junction semiconductor layer 103 in a state of being apt to cause pinholes
because of its internal stress or/and the foregoing minute dusts.
In any of these cases, a short-circuited portion comprising the pinhole
106a or/and a short-circuited portion comprising the pinhole 106b is
caused. Because of this, when a transparent and conductive thin film 104
is formed on the pin junction semiconductor layer 103, the resulting
transparent and conductive thin film 104 is short-circuited with the
conductive thin film 102b of the conductive substrate 102 through such a
pinhole.
Now, in the case of preparing a large area solar cell having a pin junction
semiconductor layer comprising a non-single crystal silicon material such
as amorphous silicon material as the photoelectric conversion layer, it is
desired to form said pin junction semiconductor layer by using a so-called
roll-to-roll type continuous plasma CVD apparatus as disclosed in U.S.
Pat. No. 4,400,409, 4,438,723 or 4,438,724.
The roll-to-roll type continuous plasma CVD apparatus comprises a plurality
of film-forming chambers being integrated while isolating one from the
other through respective isolating means, wherein each deposition chamber
is capable of continuously forming a deposited semiconductor film of n-,
i- or p-type on a lengthy and wide substrate web by causing glow discharge
in the presence of appropriate film-forming raw material gas therein while
transporting said substrate web through each of said plurality of
deposition chambers in the lengthwise direction.
Hence, it is possible to continuously form an element provided with one or
more semiconductor junctions on a large area substrate in the above
mentioned roll-to-roll type continuous plasma CVD apparatus.
As above described, the present invention makes it possible to always
provide a practically usable solar cell while repairing a defective solar
cell provided with one or more short-circuited portions if such defective
solar cell has resulted.
Shown in FIG. 2 is an apparatus which is suitable for practicing the method
of repairing such a defective solar cell as previously described according
to the present invention.
In FIG. 2, numeral reference 200 stands for the entire apparatus. Numeral
reference 201 stands for a solar cell being positioned on a mounting table
202 as the substrate holding means. The mounting table 202 is structured
such that it can horizontally move back and forth in respective arrow
directions shown by either A or B. Numeral reference 203 stands for a
probe being arranged over the solar cell 201. The probe 203 is
electrically connected to a high AC voltage-outputting power source 204 as
the voltage applying means. The AC voltage-outputting power source 204
(voltage applying means) is provided with a control circuit (not shown in
the figure). The probe 203 is so designed that it can horizontally move
back and forth in the respective arrow directions shown by B along a guide
rail 205 being arranged at the position above the solar cell 201 by the
action of a scanning means (not shown in the figure). The direction of A
is rectangular, that is, perpendicular, to the direction of B. By this,
the probe 203 is made capable of scanning the entire of the surface of the
solar cell 201. Numeral reference 208 stands for a controller for
controlling the mounting table 202 to be moved in the direction as
desired. The guide rail 205 is electrically isolated from the probe 203
through an insulating material such as aluminaceramics (not shown in the
figure). This apparatus is provided with a counter electrode (not shown in
the figure) to the probe 203 such that the distance between the counter
electrode and the probe 203 can be optionally changed. The counter
electrode is electrically grounded.
A predetermined AC voltage from the AC voltage-outputting power source 204
(voltage applying means) is applied to the probe 203 upon performing
repair treatment for the solar cell 203, wherein a discharge (spark) is
caused when the probe 203 is situated above the portion of the solar cell
201 in which a short-circuited portion due to a pinhole is present.
In the above control circuit for the AC voltage-outputting power source 204
(voltage applying means), there are memorized data of predetermined
operating parameters with respect to the interrelation between (a) the
distance (L) between the probe 203 and the counter electrode and (b) the
threshold (Vth) of an AC voltage at which the discharge (spark) is caused
in an atmospheric air when the distance between the probe 203 and the
counter electrode is L.
In the following, explanation is to be made about the preparation of a
practically usable solar cell according to the present invention using the
above apparatus by illustrating a typical example.
Firstly, there is prepared a solar cell as the solar cell 201 shown in FIG.
2 by providing a stainless steel plate, for example, of 100 mm.times.100
mm in size and 1.0 mm in thickness as the base member 102a shown in FIG.
1; forming a conductive thin film comprising zinc oxide (ZnO) as the
conductive thin film 102b shown in FIG. 1 on said stainless plate by a
sputtering method; forming a pin junction amorphous silicon semiconductor
layer as the photoelectric conversion semiconductor layer 103 shown in
FIG. 1 on said conductive thin film by a plasma CVD method; and forming a
transparent and conductive thin film comprising ITO as the conductive thin
film 104 shown in FIG. 1 on said pin junction amorphous silicon
semiconductor layer by a vacuum evaporation method.
The solar cell 201 thus obtained is positioned on the mounting table 202 of
the apparatus 200 shown in FIG. 2, wherein the conductive substrate 102 of
the solar cell 201 is electrically grounded. Then, the probe 203 is
positioned above the solar cell 201 while leaving a distance of about 5.0
mm between the top of the probe 203 and the surface of the solar cell 201.
Predetermined data with respect to the foregoing distance (L) are inputted
in the control circuit (L) for the AC voltage-outputting power source 204
(voltage applying means) so as to enable it to adjust the AC voltage to be
applied to the probe 203 upon causing the foregoing discharge (spark)
between the probe 203 and the counter electrode through the solar cell
201. Successively, the probe 203 is positioned such that it is situated at
the position right above a corner of the solar cell 201. Then, the AC
voltage from the AC voltage-outputting power source 204 (voltage applying
means) is raised to a level corresponding to the foregoing threshold
voltage. By operating the controller, the solar cell 201 on the mounting
table 202 is then continuously moved horizontally and back and forth in
the arrow directions of B, wherein every time when the probe 203 arrives
at an end indicated by 210a or at the other end indicated by 210b, the
solar cell 201 is horizontally moved some millimeter in the direction of
A, whereby the surface of the solar cell 201 is scanned by the probe 203.
In this case, when the probe 203 arrives at the position above the surface
portion comprising transparent and conductive thin film of the solar cell
201 in which a short-circuited portion due to a pinhole is present, a
discharge (spark) is caused between the probe 203 applied with the
threshold voltage and said portion of the solar cell and the spark passes
therebetween because the latter is in a earthed potential state due to
said short-circuited portion, wherein said short-circuited portion is
fused to establish an electrically insulating state. On the other hand,
such a discharge (spark) is not caused for other portion of the solar cell
not containing such short-circuited portions when the probe 203 arrives at
the position above the surface of said portions of the solar cell while
applying the threshold voltage to the probe.
In this way, a defective solar cell can be easily repaired to be a
practically usable solar cell.
FIG. 3 is a schematic view illustrating the situation wherein the
short-circuited portion of the solar cell is repaired in the above. In
FIG. 3, numeral reference 301 corresponds to the foregoing solar cell 101
(the solar cell 201 in FIG. 2); numeral reference 302 corresponds to the
foregoing conductive substrate 102; numeral reference 302a corresponds to
the foregoing base member 102a comprising a stainless steel plate; numeral
reference 302b corresponds to the foregoing conductive thin film 102b
comprising a ZnO thin film; numeral reference 303 corresponds to the
foregoing photoelectric conversion semiconductor layer 103 comprising a
pin junction amorphous silicon semiconductor layer; numeral reference 304
corresponds to the foregoing transparent and conductive thin film 104
comprising an ITO film; numeral reference 306a corresponds to the
foregoing pinhole 106a; and numeral reference 306b corresponds to the
foregoing pinhole 106b. And, numeral references 307a and 307b indicate
respectively a fused product deposited at the bottom of the pinhole 306a
and a fused product deposited at the bottom of the pinhole 306b.
In the above process, when the probe 203 arrives at the position above the
surface portion (comprising the ITO transparent and conductive thin film)
of the solar cell in which a short-circuited portion comprising the
pinhole 306a or/and a short-circuited portion comprising the pinhole 306b
respectively occurring at a portion of the pin junction amorphous silicon
semiconductor layer is present while applying a predetermined AC voltage
to the probe 203, a spark discharge current is flown only through a
limited minute region of the solar cell which contains the pinhole 306a or
306b to cause a Joule heat which results in fusing the peripheries
circumscribing the pinhole (the peripheries including a portion each of
the ZnO conductive thin film 302b, the pin junction amorphous silicon
semiconductor layer 303 and the ITO transparent and conductive thin film
304), whereby depositing a fused product 307a or/and a fused product 307b
at the bottom of the pinhole 306a or/and at the bottom of the pinhole 306b
in such a state as shown in FIG. 3. As a result, the short-circuited
portion caused due to the pinhole 306a or/and the short-circuited portion
caused due to the pinhole 306b is made in an electrically insulating
state. Because of this, the resulting solar cell becomes such that
provides photovoltaic characteristics desired for a solar cell. In this
case, even if the fused product 307a or/and the fused product 307b were
deposited in a state of being in contact with the conductive thin film 302
b or the base member 302a, there is not any undesirable problem for the
resulting repaired solar cell. That is, the fused product 307a or/and the
fused product 307b is in an oxidized state or/and a nitrogenized state
because of chemical reaction with oxygen or/and nitrogen of the
atmospheric air upon their formation and has a high electrical resistivity
similar to that of a semiconductor; because of this, the density of a
leakage current which flows through such contacted portion becomes to be
more or less around the same as the density of a leakage current which
flows through the pin junction amorphous silicon semiconductor layer 303.
The probe to be used in the present invention is desired to be such that is
of a few millimeter in diameter and has a sharply pointed top. The probe
is made of a metal through which an electric current is allowed to flow
such as copper, gold, silver, iron, nickel, stainless steel, etc.
In the present invention, the distance L between the top of the probe and
the surface of a defective semiconductor device to be repaired is an
important factor. The system for practicing the repairing method of the
present invention is designed such that said distance L can be finely
adjusted depending upon the kind of the constituent of a photoelectric
conversion semiconductor layer of a defective semiconductor device to be
repaired, the voltage withstanding pressure of a semiconductor device to
be repaired, the pressure of an atmosphere wherein the repairing process
is performed, or the like. For instance, in the case where the voltage
withstanding pressure of the photoelectric conversion semiconductor layer
of a defective semiconductor device to be repaired is small, it is desired
to make the foregoing distance small and to lower the AC voltage to be
applied.
In the present invention, the above repairing method can be performed also
in an atmosphere of a reduced pressure. In this case, when the repairing
method is performed while maintaining the distance L at the same level as
in the case of performing the repairing method in an atmospheric air, it
is desired to lower the AC voltage to be applied to a value less than the
threshold voltage because the discharge commencing voltage becomes small.
The distance L between the top of the probe and the surface of a defective
semiconductor device to be repaired upon repairing said defective
semiconductor device by the repairing method of the present invention
should be properly decided on the basis of what is above described.
However, in general, said distance L is desired to be about 0.5 to about 10
mm. Likewise, as for the AC voltage to be applied, it is desired to be of
a value of some hundreds of volts to some ten thousands voltage.
In the present invention, the voltage to be applied to the probe is not
limited to the above AC voltage. Thus, it is possible to use any other
kind of voltage of DC to high frequency (some hundreds kHz).
In fact, in the case where the photoelectric conversion semiconductor layer
of a defective semiconductor device to be repaired is such that is of a
high melting point and cannot be easily fused, it is desired to employ a
DC voltage. On the other hand, in the case where the photoelectric
conversion semiconductor layer of a defective semiconductor device to be
repaired is such that can be easily fused, it is desired to employ an AC
voltage.
The AC voltage can be of an appropriate waveform such as sine wave,
rectangular wave, exponential wave, or the like.
As for the current density of an electric current flown from the probe
during the repairing process, it should be properly decided while having
due regards on the size of a pinhole present in a defective semiconductor
device to be repaired, the constituent of the photoelectric conversion
semiconductor layer of said semiconductor device, leakage current of said
semiconductor device, and other related factors. However, in general, it
is desired to be of a value of about 0.01 to about 100 A/cm.sup.2.
Further, as for the pressure of an atmosphere wherein the repairing method
of the present invention is performed, it can be an atmospheric pressure
in a usual case.
However, in the case of incorporating oxygen atoms or/and nitrogen atoms
into the resulting fused product such as the fused product 307a or 307b
shown in FIG. 3 to thereby increase its electrical resistivity, it is
desired to perform the repairing method of the present invention in an
atmosphere of reduced pressure. As for the apparatus to be employed in
this case, it can be a substantially enclosed apparatus comprising the
entire of the apparatus shown in FIG. 2 being housed in a hermetically
sealed vessel and which is provided with an evacuating system including a
vacuum pump. In this case, the repairing method of the present invention
is performed in said apparatus while introducing gas containing oxygen
atoms or/and nitrogen atoms into the hermetically sealed vessel and
maintaining the inner pressure at a desired vacuum degree by operating the
evacuating system.
As the oxygen atom-containing gas usable in this case, there can be
illustrated O.sub.2, O.sub.3, CO.sub.2, CO, NO, NO.sub.2, etc. These gases
may be diluted with an appropriate dilution gas such as Ar, He, Ne,
H.sub.2, etc. upon introducing them into the above hermetically sealed
vessel.
Likewise, as the nitrogen-containing gas usable in this case, there can be
illustrated N.sub.2, NO, NO.sub.2, etc. As well as in the case of the
oxygen-containing gas, these nitrogen-containing gases may be diluted with
an appropriate dilution gas such as Ar, He, Ne, H.sub.2, etc. upon
introducing them into the above hermetically sealed vessel.
Shown in FIG. 4 is a schematic view of another apparatus suitable for
practicing the repairing method of the present invention.
In FIG. 4, numeral reference 401 stands for a feed roller on which a
lengthy, or continuous, conductive substrate web 403 having a solar cell
element with an ITO transparent and conductive thin film thereon
(hereinafter referred to as solar cell web) is wound, and the feed roller
401 serves to feed the solar cell web 403. Numeral reference 402 stands
for a take-up roller which serves to take up the solar cell web 403 fed by
the feed roller 401. The solar cell web 403 is fed from the feed roller
401, followed by being transported for a certain distance in the direction
indicated by an arrow B, that is, toward the take-up roller 402 by the
action of the take-up roller 402 while being maintained in a horizontal
state by means of two positioning rollers 405a and 405b respectively
capable of moving upwards or downwards, and taken up on the take-up roller
402. Both the feed roller 401 and the take-up roller 402 are electrically
grounded. Since the rear face of the solar cell web 403 is in contact with
the feed roller 401 and also with the take-up roller 402, the solar cell
web is electrically grounded through these rollers. A plurality of probes
404 are arranged at an equal interval above the solar cell web 403 being
transported toward the take-up roller 402. Each of these probes is of the
same configuration as that of the probe 203 shown in FIG. 2. And these
probes 404 are electrically isolated one from the other by an insulator
406. Each of these probes is connected to an independent AC
voltage-outputting power source 407.
The probes 404 are arranged at an equal interval and on an identical
apparent straight line such that the direction of these probes 404 being
arranged is in parallel with a solar cell region of the solar cell web 403
and the distance between the surface of the solar cell web 403 and the top
of each of these probes 404 is identical as shown in FIG. 4.
In more detail in this respect, the probes 404 are arranged such that the
angle 0 made by the apparent straight line on which the probes 404 being
arranged and the width direction of the solar cell web 403 becomes large
and the distance between the surface of the solar cell web 403 and the top
of each of the probes 404 becomes large as much as possible.
The distance between the surface of the solar cell web 403 and the top of
each of the probes 404 can be properly adjusted by moving the positioning
rollers 405a and 405b.
The repairing method of the present invention can be properly performed in
the above apparatus, for instance, in the following manner.
That is, firstly, there is provided a solar cell element 403 with an ITO
transparent and conductive thin film thereon (hereinafter referred to as
solar cell web). The solar cell web is wound on the feed roller of the
apparatus shown in FIG. 4. Then, the solar cell web 403 is fed from the
feed roller 401, and one end of the solar cell web thus fed is fixed to
the take-up roller 402 and wound thereon. By adjusting the positioning
rollers 405a and 405b, the distance between the surface of the solar cell
web 403 and the top of each of the probes 404 is made constant at about
4.0 mm. Both the feed roller 401 and the take-up roller 402 start rotating
to transport the solar cell web 403 at a speed of 30 mm/sec in the
direction B. At the same time, each of the AC voltage outputting power
sources 407 is switched on to output about 20,000 volt. During this
process, a spark (discharge) is intermittently caused at the portion of
the solar cell web 403 being transported. By this, it can be recognized
that portions of the solar cell web 403 in which short-circuited portions
due to pinholes occurring at the photoelectric conversion semiconductor
layer are repaired.
The repairing process in this case is terminated when the entire of the
solar cell web 403 is wound on the take-up roll 402, wherein the AC
voltage-outputting power source is switched off and the rotation of each
of the feed roller 401 and the take-up roller 402 is stopped. Then, the
resultant solar cell web is taken out.
Shown in FIG. 5 is a further apparatus suitable for practicing the
repairing method of the present invention. The apparatus shown in FIG. 5
is of the constitution that part of the apparatus shown in FIG. 4 is
housed in a hermetically sealed vessel (hereinafter referred to as vacuum
vessel). The repairing method of the present invention using this
apparatus is performed in an atmosphere of reduced pressure while
introducing gas containing oxygen atoms or/and nitrogen atoms into the
hermetically sealed vessel. The constitution shown in the space encircled
by a broken line C is similar to the constitution of the apparatus shown
in FIG. 4.
In FIG. 5, numeral reference 503 stands for a vacuum vessel in which a feed
roller 505 for feeding a solar cell web 504; a take-up roller 506 for
taking up the solar cell web 504 fed from the feed roller 505; a plurality
of probes 508 being arranged above the surface of the solar cell web (each
of the probes 508 being separately connected to an identical AC
voltage-outputting power source 502 being situated outside the vacuum
vessel 503); and a pair of positioning rollers are contained. The vacuum
vessel 503 is provided with a vacuum gage 518. The vacuum vessel 503 is
provided with an exhaust pipe being connected through an exhaust valve 509
to an exhaust system containing a rotary pump 512 and a mechanical booster
pump 513. Numeral reference 517 stands for a leak valve mounted to a leak
pipe being connected to the vacuum vessel 503. Numeral reference 516
stands for a reservoir provided with a header valve which contains a
gaseous mixture comprising O.sub.2 gas and Ar gas which is connected
through a gas feed pipe 514 to the vacuum vessel 503. The gas feed pipe
514 is provided with a mass flow controller 515 and an inlet valve 510.
The repairing method of the present invention using the apparatus shown in
FIG. 5 is performed, for instance, in the following manner.
That is, firstly, there is provided a solar cell element 504 with an ITO
transparent and conductive thin film thereon (hereinafter referred to as
solar cell web). The solar cell web 504 is introduced into the vacuum
vessel 503 and it is wound on the feed roller 505. Then, the solar cell
web 504 is fed from the feed roller 505, and one end of the solar cell web
thus fed is fixed to the take-up roller 506 and wound thereon. By
adjusting the positioning rollers 507, the distance between the surface of
the solar cell web 403 and the top of each of the probes 404 is made
constant at about 2.0 mm. Then, the vacuum vessel 503 is hermetically
closed. Confirming that the exhaust valve 509, the inlet valve 510, the
header valve 511 and the leak valve 517 are closed, the rotary pump 512 is
actuated, and the exhaust/valve 509 and the inlet valve 510 are gradually
opened. When the reading on the vacuum gage 518 reaches about 10 Torr, the
mechanical booster pump 513 is actuated to sufficiently evacuate the
inside of the vacuum vessel 503 through the gas feed pipe 514 including
the mass flow controller 515 to a vacuum of less than 10 mTorr. Then, the
header valve of the gas reservoir 516 is opened, and the flow rate of the
gaseous mixture from the gas reservoir 516 is made to be about 100 sccm by
adjusting the mass flow controller 515. Thereafter, both the feed roller
505 and the take-up roller 506 start rotating to transport the solar cell
web 504 at a speed of 30 mm/sec in the lengthwise direction of the solar
cell web. At the same time, the AC voltage outputting power sources 502 is
switched on to apply a predetermined voltage to each of the probes 508.
During this process, a spark (discharge) is intermittently caused at the
portion of the solar cell web 504 being transported. By this, it can be
recognized that portions of the solar cell web 504 in which
short-circuited portions due to pinholes occurred at the photoelectric
conversion semiconductor layer are present are repaired.
The repairing process in this case is terminated when the entire of the
solar cell web 504 is wound on the take-up roll 506, wherein the AC
voltage-outputting power source is switched off and the rotation of each
of the feed roller 505 and the take-up roller 506 is stopped. At the same
time, the valves 510 and 509 are closed, and the leak valve 517 is
gradually opened to thereby return the inside of the vacuum vessel 503 to
atmospheric pressure. Then, the resultant solar cell web is taken out.
The semiconductor device repaired according to the present invention is
subjected to finalizing treatments such as wiring, packaging with the use
of an insulating member, and the like, to obtain a semiconductor device
product.
For instance, in the case where a large area solar cell web has been
repaired, it is cut into a plurality of solar cell elements respectively
of a predetermined size, each of the resultant solar cell elements is
applied with a collecting electrode (105 in FIG. 1) to the surface of the
transparent and conductive thin film (104 in FIG. 1), and they are
integrated to obtain a plurality of solar cell modules.
Likewise, in the case where a semiconductor device has been repaired for
use in photosensor, the resultant is applied with a passivation film to
the surface thereof, which is then mounted on a support member for
photosensor together with a light source, lens, etc.
The present invention will be described more specifically while referring
to the following examples, but the present invention is not to be limited
in scope by these examples.
EXAMPLE 1
In this example, description is to be made about the case where the
repairing method of the present invention is applied in repairing a pin
junction amorphous silicon solar cell device having one or more
short-circuited portions, using the apparatus shown in FIG. 2.
Firstly, there was provided a stainless steel plate of 100 mm.times.100 mm
in size and 1.0 mm in thickness. This stainless steel plate was well
cleaned in a cleaning vessel. The resultant cleaned stainless steel plate
was used as the base member of the pin junction amorphous silicon solar
cell device.
On the stainless steel plate as the base member was formed a 1.0 .mu.m
thick ZnO transparent electrode by a vacuum evaporation method.
Successively, an about 0.5 .mu.m thick pin junction amorphous silicon
semiconductor layer was formed on the previously formed ZnO transparent
electrode by a plasma CVD method. Then, on the pin junction amorphous
silicon semiconductor layer thus formed was formed an about 0.07 .mu.m
thick ITO transparent and conductive thin film by a vacuum evaporation
method. In this way, there were prepared a number of pin junction
amorphous silicon solar cell elements.
As for each of the resultant pin junction amorphous silicon solar cell
elements, its current/voltage characteristics in a dark state were
examined by a conventional method. As a result, more than twenty of the
pin junction amorphous silicon solar cell elements thus obtained were such
that exhibit such characteristics shown in FIG. 6(A). From this result, it
was found that these pin junction amorphous silicon solar cell elements do
not exhibit diode characteristics and because of this, they are such that
have one or more short-circuited portions as shown in FIG. 1.
Thus, twenty of those defective pin junction amorphous silicon solar cell
elements were randomly selected. And each of them was positioned on the
mounting table 202 of the apparatus shown in FIG. 2, and it was repaired
in the same manner as described in the case of performing the repairing
method using this apparatus, wherein the distance L between the top of the
probe 203 and the surface of the ITO transparent and conductive thin film
of the pin junction amorphous silicon solar cell element was maintained
constant at 5.0 mm, and the AC voltage-outputting power source 208 was
adjusted to apply about 20,000 volt to the probe 203 in a state of not
causing discharge (spark). The travelling speed of the probe 203 was made
to be 25 mm/sec., whereas the mounting table 202 was moved at a speed of
5.0 mm/sec. intermittently every four seconds. The foregoing twenty
defective pin junction amorphous silicon solar cell elements were thus
repaired. As for each of the resultant twenty pin junction amorphous
silicon solar cell elements thus repaired, its current/voltage
characteristics in a dark state were examined. As a result, it was found
that any of the twenty repaired pin junction amorphous silicon solar cell
elements exhibits such desirable diode characteristics as shown in FIG.
6(B). It was also found as for each of the twenty repaired pin junction
amorphous silicon solar cell elements that the repaired portions are in
such a desirable state as shown in FIG. 3.
On the ITO transparent and conductive thin film of each of the foregoing
twenty repaired pin junction amorphous silicon solar cell elements was
formed a 1.0 um thick Ag collecting electrode of the configuration
indicated by numeral reference 701 in FIG. 7 by a vacuum evaporation
method, to thereby obtain twenty pin junction amorphous silicon solar cell
devices.
As for each of the resultants, its current/voltage characteristics in a
dark state were examined. As a result, it was found that any of the
resultant twenty pin junction amorphous silicon solar cell devices are
satisfactory in current/voltage characteristics.
Further, each of the resultant twenty pin junction amorphous silicon solar
cell devices was allowed to stand outdoors for two months. And its
current/voltage characteristics in a dark state were examined. As a
result, eighteen of the twenty solar cell devices were still satisfactory
in current/voltage characteristics.
As for each of the twenty pin junction amorphous silicon solar cell
devices, it was subjected to measurement of photoelectric conversion
efficiency under irradiation of AM 1.5 light.
As a result, it was found that the foregoing eighteen pin junction
amorphous silicon solar cell devices provide a satisfactory photoelectric
conversion efficiency of more than 10%.
COMPARATIVE EXAMPLE 1
Firstly, there was provided a stainless steel plate of 100 mm.times.100 mm
in size and 1.0 mm in thickness. This stainless steel plate was well
cleaned in a cleaning vessel. The resultant cleaned stainless steel plate
was used as the base member of the pin junction amorphous silicon solar
cell device.
On the stainless steel plate as the base member was formed a 1.0 .mu.m
thick ZnO transparent electrode by a vacuum evaporation method.
Successively, an about 0.5 .mu.m thick pin junction amorphous silicon
semiconductor layer was formed on the previously formed ZnO transparent
electrode by a plasma CVD method. Then, on the pin junction amorphous
silicon semiconductor layer thus formed was formed an about 0.07 .mu.m
thick ITO transparent and conductive thin film by a vacuum evaporation
method. Thus, there was obtained a pin junction amorphous silicon solar
cell element.
The above procedures were repeated, to thereby obtain twenty pin junction
amorphous silicon solar cell elements in total.
As for each of the resultant twenty pin junction amorphous silicon solar
cell elements, its current/voltage characteristics in a dark state were
examined by a conventional method. As a result, it was found that nine of
the twenty pin junction amorphous silicon solar cell elements do not
exhibit diode characteristics and because of this, they have one or more
short-circuited portions as shown in FIG. 1.
As for the remaining eleven pin junction amorphous silicon solar cell
elements, it was found that they are not so good in diode characteristics.
As for each of these eleven pin junction amorphous silicon solar cell
elements, on the ITO transparent and conductive thin film was formed a 1.0
.mu.m thick Ag collecting electrode of the configuration indicated by
numeral reference 701 in FIG. 7 by a vacuum evaporation method, to thereby
obtain a pin junction amorphous silicon solar cell device. Thus, there
were obtained eleven pin junction amorphous silicon solar cell devices in
total.
As for each of the resultant eleven pin junction amorphous silicon solar
cell devices, its current/voltage characteristics in a dark state were
examined. As a result, it was found that they are inferior to the pin
junction amorphous silicon solar cell devices obtained in Example 1 in
view of diode characteristics.
Further, each of the eleven pin junction amorphous silicon solar cell
devices was allowed to stand outdoors for two months. And its
current/voltage characteristics in a dark state were examined. As a
result, only four of the eleven solar cell devices were still practically
acceptable in view of current/voltage characteristics.
As for each of the eleven pin junction amorphous silicon solar cell
devices, it was subjected to measurement of photoelectric conversion
efficiency under irradiation of AM 1.5 light.
As a result, it was found that any of the eleven pin junction amorphous
silicon solar cell devices provides a practically acceptable photoelectric
conversion efficiency.
A mean value among the photoelectric conversion efficiencies of the eleven
pin junction amorphous silicon solar cell devices was calculated. And the
mean value was compared with the mean value among the photoelectric
conversion efficiencies of the twenty pin junction amorphous silicon solar
cell devices obtained in Example 1.
As a result, it was found that the mean value of Example 1 is surpassing
the mean value of Comparative Example 1 by 1.33 holds.
EXAMPLE 2
In this example, description is to be made about the case where the
repairing method of the present invention is applied in repairing a pin
type amorphous silicon diode photosensor having one or more
short-circuited portions, using the apparatus shown in FIG. 2.
FIG. 8 is a schematic cross-section view of the configuration of the
photosensor.
In FIG. 8, numeral reference 801 stands for the entire photosensor chip.
The photosensor chip 801 comprises a conductive substrate comprising a
base member 802a (a glass plate) and a conductive thin film electrode 802b
being disposed on said glass plate; a pin type amorphous silicon
semiconductor layer 803 being disposed on said conductive substrate; and a
transparent and conductive thin film electrode 804 being disposed on said
pin type amorphous silicon semiconductor layer. Numeral reference 805
stands for a leading electrode disposed on the transparent and conductive
thin film electrode 804. Numeral reference 806 stands for a lead frame.
Firstly, there was provided a glass plate of 100 mm.times.100 mm in size
and 1.0 in thickness as the base member 802a. This glass plate was well
cleaned in a cleaning vessel. On the glass plate thus cleaned was formed a
1.0 .mu.m thick aluminum conductive film as the conductive thin film
electrode 802b by a vacuum evaporation method. Then, the resultant was
subjected to photolithography whereby the conductive thin film was
patterned to be such a configuration as shown by numeral reference 901 in
FIG. 9(A). Successively, an about 0.8 .mu.m thick pin type amorphous
silicon semiconductor layer was formed thereon by a plasma CVD method. On
the pin type amorphous silicon semiconductor layer thus formed was formed
an about 0.07 .mu.m thick ITO transparent and conductive film as the
transparent and conductive thin film electrode 804 by a vacuum evaporation
method, to thereby obtain a photosensor element.
The resultant photosensor element was positioned on the mounting table 202
of the apparatus shown in FIG. 2, and it was subjected to repairing
treatment in the same manner as described in the case of performing the
repairing method using this apparatus, wherein the distance L between the
top of the probe 203 and the surface of the ITO transparent and conductive
thin film of the photosensor element was maintained constant at 3.0 mm,
and the AC voltage-outputting power source 208 was adjusted to apply about
20,000 volt to the probe 203 in a state of not causing discharge (spark).
The travelling speed of the probe 203 was made to be 25 mm/sec., whereas
the mounting table 202 was moved at a speed of 5.0 mm/sec intermittently
every four seconds.
The photosensor element thus treated was subjected to photolithography
thereby patterning the pin type amorphous silicon semiconductor layer and
the ITO transparent and conductive thin film electrode to be such a
configuration as shown by numeral reference 902 in FIG. 9(B).
Then, on the ITO transparent and conductive thin film electrode thus
patterned was formed an Ag thin film of the configuration shown by numeral
reference 903 in FIG. 9(C) as the leading electrode 805 by a vacuum
evaporation method. The resultant was cut into thirty six chips. Lead
frames 806 were attached to each of the thirty six chips. Thus, there were
obtained thirty six diode type photosensors.
As for each of the resultant diode type photosensors, its current/voltage
characteristics in a dark state were examined. As a result, thirty five of
the thirty six diode type photosensors exhibited a good S/N ratio. As for
each of the thirty five diode type photosensors which exhibited a good S/N
ratio, spectral-response characteristics were examined. As a result, all
of these thirty five diode type photosensors were found to be excellent in
the spectral-response characteristics required for a diode type
photosensor.
COMPARATIVE EXAMPLE 2
The procedures of Example 2 were repeated, except that the repairing method
of the present invention was not performed, to thereby thirty six diode
type photosensors.
As for each of the resultant diode type photosensors, its current/voltage
characteristics in a dark state were examined. As a result, sixteen of
them were found to be short-circuited. Others were found to be practically
acceptable in view of S/N ratio.
Further, as for each of the twenty diode type photosensors which were
practically acceptable in view of S/N ratio, spectral-response
characteristics were examined. As a result, all of these twenty diode type
photosensors were found to be practically acceptable in view of
spectral-response characteristics.
EXAMPLE 3
In this example, a description is to be made about the case where the
repairing method of the present invention is applied in repairing a pin
junction amorphous silicon germanium solar cell device having one or more
short-circuited portions, using the apparatus shown in FIG. 2.
Firstly, there was provided a glass plate of 100 mm.times.100 mm in size
and 1.0 mm in thickness. This glass plate was well cleaned in a cleaning
vessel. The resultant cleaned glass plate was used as the base member of
the pin junction amorphous silicon germanium solar cell device.
On the glass plate as the base member was formed an about 0.3 .mu.m thick
Ag conductive thin film by a sputtering method. Then, on the Ag thin film
thus formed was formed an about 1.0 .mu.m thick ZnO conductive thin film
by a sputtering method. Successively, an about 0.4 .mu.m thick pin
junction amorphous silicon germanium semiconductor layer was formed on the
previously formed ZnO conductive thin film by a plasma CVD method. Then,
on the pin junction amorphous silicon germanium semiconductor layer thus
formed was formed an about 0.07 .mu.m thick ITO transparent and conductive
thin film by a vacuum evaporation method. In this way, there were prepared
a number of pin junction amorphous silicon germanium solar cell elements.
As for each of the resultant pin junction amorphous silicon germanium solar
cell elements, its current/voltage characteristics in a dark state were
examined by a conventional method. As a result, more than twenty of the
pin junction amorphous silicon germanium solar cell elements thus obtained
were such that exhibit such characteristics shown in FIG. 6(A). From this
result, it was found that these pin junction amorphous silicon germanium
solar cell elements do not exhibit diode characteristics and because of
this, they have one or more short-circuited portions as shown in FIG. 1.
Thus, twenty of those defective pin junction amorphous silicon solar cell
elements were randomly selected. And each of them was positioned on the
mounting table 202 of the apparatus shown in FIG. 2, and it was repaired
in the same manner as described in the case of performing the repairing
method using this apparatus, wherein the distance L between the top of the
probe 203 and the surface of the ITO transparent and conductive thin film
of the pin junction amorphous silicon germanium solar cell element was
maintained constant at 4.5 mm, and the AC voltage-outputting power source
208 was adjusted to apply about 30,000 volt to the probe 203 in a state of
not causing discharge (spark). The travelling speed of the probe 203 was
made to be 25 mm/sec., whereas the mounting table 202 was moved at a speed
of 5.0 mm/sec intermittently every four seconds. The foregoing twenty
defective pin junction amorphous silicon germanium solar cell elements
were thus repaired. As for each of the resultant twenty pin junction
amorphous silicon germanium solar cell elements thus repaired, its
current/voltage characteristics in a dark state were examined. As a
result, it was found that any of the twenty repaired pin junction
amorphous silicon germanium solar cell elements exhibits such desirable
diode characteristics as shown in FIG. 6(B). It was also found as for each
of the twenty repaired pin junction amorphous silicon germanium solar cell
elements that the repaired portions are in such a desirable state as shown
in FIG. 3.
On the ITO transparent and conductive thin film of each of the foregoing
twenty repaired pin junction amorphous silicon germanium solar cell
elements was formed a 1.0 .mu.m thick Ag collecting electrode of the
configuration indicated by numeral reference 701 in FIG. 7 by a vacuum
evaporation method, to thereby obtain twenty pin junction amorphous
silicon germanium solar cell devices.
As for each of the resultants, its current/voltage characteristics in a
dark state were examined. As a result, it was found that any of the
resultant twenty pin junction amorphous silicon germanium solar cell
devices are satisfactory in current/voltage characteristics.
Further, each of the resultant twenty pin junction amorphous silicon
germanium solar cell devices was allowed to stand outdoors for two months.
And its current/voltage characteristics in a dark state were examined. As
a result, nineteen of the twenty solar cell devices were still
satisfactory in current/voltage characteristics.
As for each of the twenty pin junction amorphous silicon germanium solar
cell devices, it was subjected to measurement of photoelectric conversion
efficiency under irradiation of AM 1.5 light.
As a result, it was found that the foregoing nineteen pin junction
amorphous silicon germanium solar cell devices provide a satisfactory
photoelectric conversion efficiency of more than 10%.
EXAMPLE 4
In this example, description is to be made about the case where the
repairing method of the present invention is applied in repairing a large
area pin junction amorphous silicon solar cell device having one or more
short-circuited portions, using the apparatus shown in FIG. 4.
Firstly, there was provided a lengthy stainless steel web of 50 m in
length, 10 cm in width and 0.1 mm in thickness. This stainless steel web
was well cleaned in a cleaning vessel. The resultant cleaned stainless
steel web was used as the base member of the pin junction amorphous
silicon solar cell device.
On the stainless steel web as the base member were formed an about 0.3
.mu.m thick Ag conductive thin film and then, an about 2.0 .mu.m thick
conductive thin film respectively by a sputtering method using a
conventional roll-to-roll type sputtering apparatus. Successively, an
about 0.5 .mu.m thick pin junction amorphous silicon semiconductor layer
was formed on the previously formed ZnO conductive thin film by a plasma
CVD method using a roll-to-roll type plasma CVD apparatus disclosed in
FIG. 2 of U.S. Pat. No. 4,438,724. Then, on the pin junction amorphous
silicon semiconductor layer thus formed was formed an about 0.07 .mu.m
thick ITO transparent and conductive thin film by a vacuum evaporation
method. In this way, there was formed a large area pin junction amorphous
silicon solar cell element on the lengthy stainless steel web (hereinafter
referred to as pin junction solar cell element web).
The pin junction solar cell element web was set to the apparatus shown in
FIG. 4 in the same manner as above described with respect to the repairing
method of the present invention using the apparatus shown in FIG. 4,
wherein it was treated in the same manner as above described in the case
of performing the repairing method using this apparatus wherein the
distance L between the top of each of the probes 404 and the surface of
the ITO transparent and conductive thin film of the pin junction solar
cell element web was maintained constant at 4.0 mm, and each of the AC
voltage-outputting power sources 407 was adjusted to apply about 20,000
volt to each of the probes 404 in a state of not causing discharge
(spark). The travelling speed of each of the probes 404 was made to be 30
mm/sec. The pin junction solar cell element web thus treated was taken out
from the apparatus.
Then, the pin junction solar cell element web was cut by way of a
conventional photolithography process to obtain eighty pin junction solar
cell elements respectively of 100 mm.times.100 mm in size.
On the ITO transparent and conductive thin film of each of the eighty pin
junction solar cell elements was formed an about 1.0 .mu.m thick Ag
collecting electrode of the configuration indicated by numeral reference
701 in FIG. 7 by a vacuum evaporation method, to thereby obtain eighty pin
junction amorphous silicon solar cell devices.
As for each of the resultants, its current/voltage characteristics in a
dark state were examined. As a result, it was found that any of the
resultant twenty pin junction amorphous silicon solar cell devices are
satisfactory in current/voltage characteristics.
Further, each of the resultant eighty pin junction amorphous silicon solar
cell devices was allowed to stand outdoors for two months. And its
current/voltage characteristics in a dark state were examined. As a
result, seventy six of the eighty solar cell devices were still
satisfactory in current/voltage characteristics.
As for each of the eighty pin junction amorphous silicon solar cell
devices, it was subjected to measurement of photoelectric conversion
efficiency under irradiation of AM 1.5 light.
As a result, it was found that the foregoing seventy six pin junction
amorphous silicon solar cell devices provide a satisfactory photoelectric
conversion efficiency of more than 10%.
EXAMPLE 5
As well as in the case of Example 4, description is to be made about the
case where the repairing method of the present invention is applied in
repairing a large area pin junction amorphous silicon solar cell device
having one or more short-circuited portions using the apparatus shown in
FIG. 5.
In the same manner as in Example 4, there was provided a large area pin
junction amorphous silicon solar cell element formed on a lengthy
stainless steel web (hereinafter referred to as pin junction solar cell
element web).
The pin junction solar cell element web was set to the apparatus shown in
FIG. 5 in the same manner as above described with respect to the repairing
method of the present invention using the apparatus shown in FIG. 5. Then,
the distance L between the top of each of the probes 508 and the surface
of the ITO transparent and conductive thin film of the pin junction solar
cell element web 504 was maintained constant at 2.0 mm by the positioning
rollers 507. Thereafter, the vacuum vessel 503 was evacuated to bring the
inside to a vacuum of less than 10 mTorr. The pin junction solar cell
element web 504 was treated in the same manner as above described in the
case of performing the repairing method using this apparatus while
introducing into the vacuum vessel 503 a gaseous mixture comprising
O.sub.2 and Ar (O.sub.2 /Ar=10%) at a flow rate of 100 sccm wherein the AC
voltage-outputting power sources 502 was adjusted to apply about 20,000
volt to each of the probes 508 in a state of not causing discharge (spark)
and the travelling speed of the probes 508 was made to be 30 mm/sec. The
pin junction solar cell element web thus treated was taken out from the
apparatus.
Then, the pin junction solar cell element web was cut by way of a
conventional photolithography process to obtain eighty pin junction solar
cell elements respectively of 100 mm.times.100 mm in size.
On the ITO transparent and conductive thin film of each of the eighty pin
junction solar cell elements was formed an about 1.0 .mu.m thick Ag
collecting electrode of the configuration indicated by numeral reference
701 in FIG. 7 by a vacuum evaporation method, to thereby obtain eighty pin
junction amorphous silicon solar cell devices.
As for each of the resultants, its current/voltage characteristics in a
dark state were examined. As a result, it was found that any of the
resultant twenty pin junction amorphous silicon solar cell devices are
satisfactory in current/voltage characteristics.
Further, each of the resultant eighty pin junction amorphous silicon solar
cell devices was allowed to stand outdoors for two months. And its
current/voltage characteristics in a dark state were examined. As a
result, seventy eight of the eighty solar cell devices were still
satisfactory in current/voltage characteristics.
As for each of the eighty pin junction amorphous silicon solar cell
devices, it was subjected to measurement of photoelectric conversion
efficiency under irradiation of AM 1.5 light.
As a result, it was found that the foregoing seventy eight pin junction
amorphous silicon solar cell devices provide a satisfactory photoelectric
conversion efficiency of more than 10%.
EXAMPLE 6
In this example, description is to be made about the case where the
repairing method of the present invention is applied in repairing a pin
junction amorphous silicon germanium solar cell device having one or more
short-circuited portions, using the apparatus shown in FIG. 2.
Firstly, there was provided a glass plate of 100 mm.times.100 mm in size
and 1.0 mm in thickness. This glass plate was well cleaned in a cleaning
vessel. The resultant cleaned glass plate was used as the base member of
the pin junction amorphous silicon solar cell device.
On the glass plate as the base member was formed an about 0.07 .mu.m thick
ITO transparent and conductive thin film by a vacuum evaporation method.
Successively, an about 0.4 .mu.m thick pin junction amorphous silicon
germanium semiconductor layer was formed on the previously formed ITO
transparent and conductive thin film by a plasma CVD method. Then, on the
pin junction amorphous silicon germanium semiconductor layer thus formed
was formed an about 0.3 .mu.m thick Ag conductive thin film by a
sputtering method. Finally, an about 1.0 .mu.m thick ZnO conductive thin
film on the Ag conductive thin film by a sputtering method.
In this way, there were prepared a number of pin junction amorphous silicon
germanium solar cell elements.
As for each of the resultant pin junction amorphous silicon germanium solar
cell elements, its current/voltage characteristics in a dark state were
examined by a conventional method. As a result, more than twenty of the
pin junction amorphous silicon germanium solar cell elements thus obtained
were such that exhibit such characteristics shown in FIG. 6(A). From this
result, it was found that these pin junction amorphous silicon germanium
solar cell elements do not exhibit diode characteristics and because of
this, they have one or more short-circuited portions as shown in FIG. 1.
Thus, twenty of those defective pin junction amorphous silicon germanium
solar cell elements were randomly selected. And each of them was
positioned on the mounting table 202 of the apparatus shown in FIG. 2, and
it was repaired in the same manner as described in the case of performing
the repairing method using this apparatus, wherein the distance L between
the top of the probe 203 and the surface of the ZnO conductive thin film
of the pin junction amorphous silicon germanium solar cell element was
maintained constant at 4.5 mm, and the AC voltage-outputting power source
208 was adjusted to apply about 20,000 volt to the probe 203 in a state of
not causing discharge (spark). The travelling speed of the probe 203 was
made to be 25 mm/sec., whereas the mounting table 202 was moved at a speed
of 5.0 mm/sec. intermittently every four seconds. The foregoing twenty
defective pin junction amorphous silicon germanium solar cell elements
were thus repaired. As for each of the resultant twenty pin junction
amorphous silicon germanium solar cell elements thus repaired, its
current/voltage characteristics in a dark state were examined. As a
result, it was found that any of the twenty repaired pin junction
amorphous silicon germanium solar cell elements exhibits such desirable
diode characteristics as shown in FIG. 6(B). It was also found as for each
of the twenty repaired pin junction amorphous silicon solar cell elements
that the repaired portions are in such a desirable state as shown in FIG.
3.
On the ZnO conductive thin film of each of the twenty repaired pin junction
amorphous silicon germanium solar cell elements was formed an about 1.0
.mu.m thick Ag collecting electrode of the configuration indicated by
numeral reference 701 in FIG. 7 by a vacuum evaporation method, to thereby
obtain twenty pin junction amorphous silicon solar cell devices.
As for each of the resultants, its current/voltage characteristics in a
dark state were examined. As a result, it was found that any of the
resultant twenty pin junction amorphous silicon germanium solar cell
devices are satisfactory in current/voltage characteristics.
Further, each of the resultant twenty pin junction amorphous silicon
germanium solar cell devices was allowed to stand outdoors for two months.
And its current/voltage characteristics in a dark state were examined. As
a result, nineteen of the twenty solar cell devices were still
satisfactory in current/voltage characteristics.
As for each of the twenty pin junction amorphous silicon germanium solar
cell devices, it was subjected to measurement of photoelectric conversion
efficiency under irradiation of AM 1.5 light.
As a result, it was found that the foregoing nineteen pin junction
amorphous silicon solar cell devices provide a satisfactory photoelectric
conversion efficiency of more than 10%.
COMPARATIVE EXAMPLE 3
In this comparative example, a description is to be made about the case
where the known repairing method is applied in repairing a pin junction
amorphous silicon germanium solar cell device of the same configuration as
that of the pi junction amorphous silicon germanium solar cell device in
Example 6 which has one or more short-circuited portions.
Shown in FIG. 11 is a schematic diagram of the known repairing method.
In FIG. 11, numeral reference 1100 stands for a glass plate, numeral
reference 1002 stands for an argon gas laser of 514.5 nm in oscillating
wavelength, and numeral reference 1103 stands for a photosensor having a
sensitivity to said wavelength and which outputs a signal. Numeral
reference 1104 stands for a controller which serves to control an
outputting power of the argon gas laser depending upon a signal outputted
from the photosensor 1103.
There was provided a pin junction amorphous silicon germanium solar cell
element 1100 prepared in the same manner as in Example 6. (This pin
junction amorphous silicon germanium solar cell element has one or more
pinholes.)
A glass plate 1101 of 1.0 mm in thickness was placed at the position above
the argon gas laser 1102 such that laser beam from the argon gas laser is
irradiated to the rear face of the glass plate. The photosensor 1103 was
arranged so as to be situated over the optical path of the laser beam from
the argon gas laser 1102. Then, the pin junction amorphous silicon
germanium solar cell element 1100 (hereinafter referred to as pin junction
solar cell element 1100, in short) was positioned on the glass plate 1101
in the way as shown in FIG. 11. (The glass plate 1101 is designed such
that it can horizontally move to either side by means of a manipulator
(not shown in the figure) to allow the laser beam from the argon gas laser
1102 to be irradiated to an optional position of the pin junction
amorphous silicon germanium semiconductor layer of the pin junction solar
cell element 1100.)
Numeral reference 1105 stands for a pinhole occurring at the pin junction
amorphous silicon germanium semiconductor layer which was previously
detected by a scanning electron microscope. (FIG. 12 is a schematic
explanatory view of this pinhole, wherein numeral reference 1202 stands
for a transparent and conductive substrate having a pin junction amorphous
silicon germanium semiconductor layer with a pinhole 1200 being disposed
thereon.)
Then, the argon gas laser 1102 was actuated to oscillate the laser beam,
wherein the glass plate was moved to allow the laser beam to be irradiated
through the pinhole 1105 to the photosensor 1103; and the controller 1104
was adjusted to reduce the outputting power of the argon gas laser 1102 to
a detection limit of the photosensor 1103.
Successively, the outputting power of the argon gas laser 1102 was raised
by adjusting the controller 1104 to fuse the periphery of the pinhole
1105, whereby the pinhole 1105 was filled up with the constituent of the
pin junction amorphous silicon germanium semiconductor layer in a state
shown by numeral reference 1203 in FIG. 12.
Independently, with respect to this known repairing method, observation was
made about whether it is possible to perform detection and repairs of a
pinhole of the pin junction amorphous silicon germanium semiconductor
layer at the same time as in the present invention.
That is, the above known repairing system was modified such that the entire
surface region of the pin junction solar cell element 1100 can be scanned
by a manipulator (not shown in the figure) while horizontally moving the
glass plate 1101 at a speed of 1.0 mm/sec in order for pinholes of the pin
junction amorphous silicon germanium semiconductor layer to be detected by
the photosensor 1103; and the controller 1104 is programed such that the
manipulator is terminated and the outputting power of the argon gas laser
1102 is raised when such pinholes could be detected by the photosensor
1103. Using this modified system, detection and repairs of one or more
pinholes of a pin amorphous silicon germanium solar cell element were
tried to be performed at the same time as in the case of the present
invention. As a result, it was found that it is almost impossible to
perform detection and repairs of a pinhole of the pin junction amorphous
silicon germanium semiconductor layer at the same time, because the
foregoing laser beam passes through the pinhole but is substantially
absorbed by the pin junction amorphous silicon germanium semiconductor
layer with no such pinhole.
Now, on the pin junction solar cell element repaired in the above in
accordance with the known repairing method, an about 1.0 .mu.m thick ZnO
conductive thin film was formed by a sputtering method. Successively, on
the ZnO conductive thin film was formed an about 0.3 .mu.m thick Ag thin
film by a sputtering method. In this way, there were prepared twenty pin
junction amorphous silicon germanium solar cell devices.
As for each of the resultants, its current/voltage characteristics in a
dark state were examined. As a result, it was found that only twelve of
the resultant twenty pin junction amorphous silicon germanium solar cell
devices are practically acceptable in view of current/voltage
characteristics.
Further, each of the foregoing twelve pin junction amorphous silicon
germanium solar cell devices (which were practically acceptable in view of
current/voltage characteristics) was allowed to stand outdoors for two
months. And its current/voltage characteristics in a dark state were
examined. As a result, only six of the twelve solar cell devices were
still practically acceptable in view of current/voltage characteristics.
As for each of the foregoing six pin junction amorphous silicon germanium
solar cell devices, it was subjected to measurement of photoelectric
conversion efficiency under irradiation of AM 1.5 light.
As a result, it was found that the foregoing six pin junction amorphous
silicon solar cell devices provide a photoelectric conversion efficiency
of less than 9%.
As apparent from what is above described, the present invention provides
various significant advantages which can not be easily expected by the
prior art. That is, (i) a plurality of pinholes present in a large
semiconductor device can be entirely repaired by a simple process without
hindering the quality of the semiconductor device and because of this, the
yield of a semiconductor device is markedly improved; (ii) since detection
and repairs of such pinholes are performed at the same time, it is not
necessary to perform detection of the spatial location of such pinholes
prior to commencing the repairing process as in the prior art; (iii) the
entire process of repairing such pinholes is performed under dry
environment without such a time-consuming complicated process including a
water-treating step and a drying step as in the prior art and because of
this, the period of time required for the production of a semiconductor
device is markedly shortened; (iv) a desirable semiconductor device can be
efficiently produced without the problems of reducing the quality thereof
with corrosion by water, alkaline materials, etc.; and (v) the cost of a
semiconductor device can be eventually reduced.
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